CN103805726B - A kind of method using rotary hearth furnace pearl iron process to fully utilize iron red mud - Google Patents
A kind of method using rotary hearth furnace pearl iron process to fully utilize iron red mud Download PDFInfo
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Abstract
The invention discloses a kind of method utilizing rotary hearth furnace pearl iron process to fully utilize iron red mud, relate to the recycling of the extraction of iron in iron red mud, enrichment and red mud, it is characterized in that utilizing iron red mud, carbonaceous reducing agent and additive for raw material, obtain pearl iron and molten point slag through operations such as batching, mixing, pelletizing, molten point of rotary hearth furnace reduction, fragmentation, magnetic separation.The pearl iron produced can do the raw material of electric furnace or converter steelmaking, and molten point hydrochloric acid for dreg leaches and extracts scandium, and leached mud is used as cement additire.This method can make full use of red mud resource, realizes the zero release comprehensive reutilization of refuse, has good economic and social benefit.
Description
Technical field
The invention belongs to ironmaking field, relate to the rotary hearth furnace comprehensive utilization method of iron red mud and the comprehensive reutilization for red mud thereof.
Background technology
Red mud is Al
2o
3the industrial solid castoff of discharging in production process, also contains the multiple rare and scatter element such as Sc, Ga, In and certain alkali number except containing except Fe, Al, Si in red mud.Chinese Al in 2010
2o
3output is about 2,900 ten thousand tons, and red mud quantity discharged is 4500 ~ 5,000 ten thousand tons, on average often produces 1 ton of Al
2o
3by-product red mud 1.0 ~ 1.8 tons, red mud accumulation quantity discharged reaches several hundred million ton, and current red mud is mostly built a dam and stored up, and build a dam and store up not only somewhat expensive, waste resource, also can cause the pollution of environment, building a dam in addition to store up also exists certain potential safety hazard.Along with the development of aluminum oxide industry, discharge and the harm of red mud have become day by day serious problem.
Scandium is scattered in many mineral, and content is few, and mineral are complicated, are a kind of important rare earth elements.Very difficult to the separation and Extraction of metal scandium, and the amount of metal extracted is little, expensive.Scandium is owing to having exclusive characteristic, and over nearly 20 years, it has good application in new type electro source material, laserable material, alloy addition and metal modifiers.These have been widely used in the fields such as space flight, nuclear energy, metallurgy and military project containing scandium material, and development is very fast, has good prospects.
The thinking that utilizes at present for iron red mud is generally first carry iron to fully utilize bits again, but in iron red mud, the separation of slag iron still also exists problem.The research of reclaiming iron from iron red mud is a lot, such as application number be 200910044285.8 Chinese patent application disclose a kind of method reclaiming iron ore concentrate from alumina laterite, in first using, magnetic machine reclaims ferromagnetism iron ore concentrate, the mine tailing obtained reclaims weak magnetism concentrate through high gradient magnetic separator again, after ferromagnetism iron ore concentrate and weak magnetism concentrate being merged, dehydration obtains iron ore concentrate, TFe >=54% of iron ore concentrate, the rate of recovery of Fe is 28 ~ 35%.Application number be 200510200493.4 Chinese patent application disclose a kind of method extracting iron and aluminium from high-iron bauxite, the method adopt sintering, blast-furnace smelting, due to Al in slag
2o
3content cause blast furnace normally to produce up to 32 ~ 36%.Application number is a kind of method that the Chinese patent application of 200510200559.X discloses recovering iron from red mud, red mud mixes with coal and iron sponge powder, rotary kiln reducing roasting is together added with industrial coal after compression-molded dry, magnetic separation operation is sent after cooling, extrusion molding after the iron sponge powder obtained mixes with binding agent and unslaked lime, drying, obtain ball block product.Application number be 201210022603.2 Chinese patent application disclose a kind of processing method of producing reduced iron from red mud, red mud and promotor are mixed and made into pressed compact by a certain percentage, pressed compact and reductive agent are loaded reductive jar and reinstalls kiln car, kiln car is utilized tunnel furnace roasting 20 ~ 50 hours between 1100-1300 DEG C, in finished product, Fe content is 73%.It is to be modified that above-mentioned patent application also exists high, the inefficient shortcoming of power consumption etc.
Summary of the invention
In order to overcome above-mentioned technical problem, the invention provides a kind of iron red mud method of comprehensive utilization of technically feasible, reasonable in economy, thus making full use of the iron red mud resource of China.
Method of the present invention comprises:
1) iron red mud after oven dry, carbonaceous reducing agent, additive mixing are obtained compound, wherein the amount of allocating into of carbonaceous reducing agent is 10 ~ 20% of red mud, and the amount of allocating into of additive is 1 ~ 3% of compound;
2) add in compound account for compound weight ratio 8 ~ 12% water, make pelletizing after mixing, dry for standby;
3) in advance at the carbon dust that bottom refractory upper berth one deck 3 ~ 5mm is thick, and by dry after pelletizing individual layer or double bunk on the bottom refractory of rotary hearth furnace, temperature in rotary hearth furnace is 1350 ~ 1450 DEG C, recovery time is 10 ~ 20min, through overcooling, fragmentation, magnetic separation after pelletizing eliminating, final acquisition carbon content is the pearl iron that can be used for making steel and the Sc of 1 ~ 3%
2o
3grade is at molten point slag two kinds of products of 150 ~ 230ppm;
4) in acid tolerance response tank, add the hydrochloric acid of 18 ~ 30%, then add molten point slag, liquid-solid ratio is 8:1, and temperature of reaction is 50 ~ 80 DEG C, reacts after 1 ~ 3 hour and filters, and can be the leach liquor of 23 ~ 28mg/L containing scandium, leaching yield be more than 90%.
The all iron content of described iron red mud between 25 ~ 52%, Sc
2o
3content is 50 ~ 150ppm, Al
2o
3content is 15 ~ 25%, SiO
2content is 5 ~ 10%, TiO
2content is 3% ~ 10%, CaO content is 1 ~ 5%, Na
2o content is 4 ~ 8%, and surplus is the material of the easy scaling loss such as some crystal water;
Described carbonaceous reducing agent is coal dust or coke powder, and fixed carbon content is more than 80%, and ash content is below 10%, and granularity is less than 80 orders;
Described additive comprises CaO, CaF
2, Na
2cO
3, this area can regulate its consumption according to red mud and carbonaceous reducing agent composition.
In described step 3), the molten point temperature of reduction is 1350 ~ 1450 DEG C, and the reduction molten point time is 10 ~ 20min.
In described step 4), concentration of hydrochloric acid is 18 ~ 30%, and liquid-solid ratio is 8:1, and temperature of reaction is 50 ~ 80 DEG C, and the reaction times is 1 ~ 3 hour.
The invention is characterized in rotary hearth furnace to be major equipment, utilize iron red mud, carbonaceous reducing agent and additive for raw material, through the operations such as batching, mixing, agglomeration, molten point of rotary hearth furnace reduction, fragmentation, magnetic separation obtain carbon content be 1 ~ 3% pearl iron and scandium content be that melting of 150 ~ 230ppm divides a slag, molten point slag acidleach is obtained the leach liquor containing scandium 23 ~ 28mg/L, and leached mud is used as cement additire.
This invention take rotary hearth furnace as major equipment, and utility appliance comprises feeding system, feed bin, belted electronic balance, mixer, pelletizer, dryer, discharging machine, crusher, magnetic separator and Belt Conveying equipment, the leaching plants such as acidproof tank.
Advantage of the present invention is:
(1) make slag iron in iron red mud be separated completely, so can be iron red mud comprehensive utilization take a firm foundation.
(2) be primary reducing agent with coal, meet the energy structure of China.
(3) be that major equipment carries out slag sluicing system with rotary hearth furnace, advanced technology, produce flexibly, cost is low, strong adaptability, is applicable to building near red mud dam, saves transportation cost.
(4) in molten point slag, iron level is less, can reduce follow-up acid leaching process acid consumption, reduce production cost.
Accompanying drawing explanation
Fig. 1 is the principle process of present invention process
Embodiment
Following embodiment is explanation of the invention instead of restriction.
This invention take rotary hearth furnace as major equipment, and utility appliance comprises feeding system, feed bin, belted electronic balance, mixer, pelletizer, dryer, discharging machine, crusher, magnetic separator and Belt Conveying equipment, the leaching plants such as acidproof tank.Concrete production process is:
Material condition is: all iron content of iron red mud, between 25 ~ 52%, is converted into ferriferous oxide content between 38 ~ 74%, Sc
2o
3grade between 50 ~ 150ppm, Al
2o
3content is 15 ~ 25%, SiO
2content is 5 ~ 10%, TiO
2content is 3% ~ 10%, CaO content is 1 ~ 5%, Na
2o content is 4 ~ 8%, and surplus is the material of the easy scaling loss such as some crystal water.
Carbonaceous reducing agent is coal dust or coke powder, fixed carbon content more than 80%, ash content below 10%, granularity is less than 80 orders.
Additive is CaO, CaF
2, Na
2cO
3.
Technical process is:
(1) red mud, carbonaceous reducing agent, additive mixer are mixed, wherein the amount of allocating into of reductive agent is 10 ~ 20% of red mud, the amount of allocating into of additive is 1 ~ 3% of total stuff amount;
(2) water yield of adding is 8 ~ 12% of compound, after mixer mixing, make pelletizing, dry for standby with pelletizer;
(3) in advance at the carbon dust that bottom refractory upper berth one deck 3 ~ 5mm is thick, after by dry after pelletizing individual layer or double bunk on the bottom refractory of rotary hearth furnace, temperature in rotary hearth furnace is 1350 ~ 1450 DEG C, recovery time is 10 ~ 20min, through overcooling, fragmentation, magnetic separation after pelletizing eliminating, final acquisition carbon content is the pearl iron that can be used for making steel and the Sc of 1 ~ 3%
2o
3grade is at molten point slag two kinds of products of 150 ~ 230ppm;
(4) in acid tolerance response tank, add the hydrochloric acid of 18 ~ 30%, then add molten point slag, liquid-solid ratio is 8:1, and temperature of reaction is 50 ~ 80 DEG C, reacts after 1 ~ 3 hour and filters, and can be the leach liquor of 23 ~ 28mg/L containing scandium, leaching yield be more than 90%.
(5) leached mud after extract technology can be used as cement additire, realizes the zero release comprehensive utilization of iron red mud.
The sulphur brought in pearl iron due to iron red mud, carbonaceous reducing agent in this technique is more, and reaction system desulfurization condition is poor, for ensureing that in pearl iron, sulphur content is relatively qualified, and must reinforcing desulfuration.As select sulfur-bearing low reductive agent, with addition of a certain amount of lime, take desulfurization etc. outside road.
After obtaining pearl iron and molten point slag, pearl iron can replace steel scrap or add converter or electric furnace as steel-making refrigerant; Sc in molten point slag
2o
3grade can reach 150 ~ 230ppm, and iron content can be used as a kind of raw material of Ore Leaching scandium less, and leached mud can be used as cement additire.
Embodiment 1
By Fe
2o
3content is that the additive of iron red mud, weight to be the coal dust of iron red mud weight 18% and weight be iron red mud and the coal dust weight summation 2% of 50.46% mixes to mixer through Belt Conveying, and regulates mixing material moisture to 10%.The mixing material mixed is made carbonaceous pelletizing through Belt Conveying to pair roller ball press, and pressure is 17MPa, and pelletizing is of a size of 40 × 30 × 21mm pillow ellipsoid.Green-ball after drying single berth on the carbon refractories of rotary hearth furnace, in advance at the carbon dust that carbon refractories upper berth one deck 3 ~ 5mm is thick.Temperature in rotary hearth furnace is 1350 ~ 1450 DEG C, and pelletizing residence time in rotary hearth furnace is 10 ~ 20 minutes, is then discharged at discharge port by discharging machine.The product of discharging sends into magnetic separator magnetic separation after cooling, fragmentation, and after choosing, magnetic substance is pearl iron, and non-magnetic substance is molten point slag.Its composition is in table 1,2,3.In acid tolerance response tank, add the hydrochloric acid 400L that concentration is 30%, then add 50kg molten point of slag, be heated to 60 DEG C, react after 1.5 hours and filter, obtain scandium content be 24.4mg/L contain scandium leach liquor 350L, leaching yield is 93%.
The first iron red mud composition of table 1
Table 2 pearl ferrous components
The molten point slag ingredient of table 3
Embodiment 2
By Fe
2o
3content is that the additive of iron red mud, weight to be the coal dust of iron red mud weight 18% and weight be iron red mud and the coal dust weight summation 2% of 45.87% mixes to mixer through Belt Conveying, and regulates mixing material moisture to 10%.The mixing material mixed is made carbonaceous pelletizing through Belt Conveying to pair roller ball press, and pressure is 17MPa, and pelletizing is of a size of 40 × 30 × 21mm pillow ellipsoid.Green-ball after drying single berth on the carbon refractories of rotary hearth furnace, in advance at the carbon dust that carbon refractories upper berth one deck 3 ~ 5mm is thick.Temperature in rotary hearth furnace is 1350 ~ 1450 DEG C, and pelletizing residence time in rotary hearth furnace is 10 ~ 20 minutes, is then discharged at discharge port by discharging machine.The product of discharging sends into magnetic separator magnetic separation after cooling, fragmentation, and after choosing, magnetic substance is pearl iron, and non-magnetic substance is molten point slag.Its composition is in table 1,2,3.In acid tolerance response tank, add the hydrochloric acid 400L that concentration is 30%, then add 50kg molten point of slag, be heated to 60 DEG C, react after 1.5 hours and filter, obtain scandium content be 27.4mg/L contain scandium leach liquor 350L, leaching yield is 94%.
Table 4 the second iron red mud composition
Table 5 pearl ferrous components
The molten point slag ingredient of table 6
Embodiment 3
By Fe
2o
3content is that the additive of iron red mud, weight to be the coal dust of iron red mud weight 10% and weight be iron red mud and the coal dust weight summation 1% of 45.87% mixes to mixer through Belt Conveying, and regulates mixing material moisture to 12%.The mixing material mixed is made carbonaceous pelletizing through Belt Conveying to pair roller ball press, and pressure is 17MPa, and pelletizing is of a size of 40 × 30 × 21mm pillow ellipsoid.Green-ball after drying single berth on the carbon refractories of rotary hearth furnace, in advance at the carbon dust that carbon refractories upper berth one deck 3 ~ 5mm is thick.Temperature in rotary hearth furnace is 1350 ~ 1450 DEG C, and pelletizing residence time in rotary hearth furnace is 10 ~ 20 minutes, is then discharged at discharge port by discharging machine.The product of discharging sends into magnetic separator magnetic separation after cooling, fragmentation, and after choosing, magnetic substance is pearl iron, and non-magnetic substance is molten point slag.Its composition is in table 1,2,3.In acid tolerance response tank, add the hydrochloric acid 400L that concentration is 25%, then add 50kg molten point of slag, be heated to 80 DEG C, react after 1.5 hours and filter, obtain scandium content be 25.2mg/L contain scandium leach liquor 350L, leaching yield is 95.5%.
The third iron red mud composition of table 7
Table 8 pearl ferrous components
The molten point slag ingredient of table 9
Embodiment 4
By Fe
2o
3content is that the additive of iron red mud, weight to be the coal dust of iron red mud weight 20% and weight be iron red mud and the coal dust weight summation 3% of 45.87% mixes to mixer through Belt Conveying, and regulates mixing material moisture to 8%.The mixing material mixed is made carbonaceous pelletizing through Belt Conveying to pair roller ball press, and pressure is 17MPa, and pelletizing is of a size of 40 × 30 × 21mm pillow ellipsoid.Green-ball after drying single berth on the carbon refractories of rotary hearth furnace, in advance at the carbon dust that carbon refractories upper berth one deck 3 ~ 5mm is thick.Temperature in rotary hearth furnace is 1350 ~ 1450 DEG C, and pelletizing residence time in rotary hearth furnace is 10 ~ 20 minutes, is then discharged at discharge port by discharging machine.The product of discharging sends into magnetic separator magnetic separation after cooling, fragmentation, and after choosing, magnetic substance is pearl iron, and non-magnetic substance is molten point slag.Its composition is in table 1,2,3.In acid tolerance response tank, add the hydrochloric acid 400L that concentration is 18%, then add 50kg molten point of slag, be heated to 50 DEG C, react after 1.5 hours and filter, obtain scandium content be 28.4mg/L contain scandium leach liquor 350L, leaching yield is 90.1%.
Table 10 the 4th kind of iron red mud composition
Table 11 pearl ferrous components
The molten point slag ingredient of table 12
Embodiment 5
By Fe
2o
3content is that the additive of iron red mud, weight to be the coal dust of iron red mud weight 20% and weight be iron red mud and the coal dust weight summation 3% of 35.71% mixes to mixer through Belt Conveying, and regulates mixing material moisture to 8%.The mixing material mixed is made carbonaceous pelletizing through Belt Conveying to pair roller ball press, and pressure is 17MPa, and pelletizing is of a size of 40 × 30 × 21mm pillow ellipsoid.Green-ball after drying single berth on the carbon refractories of rotary hearth furnace, in advance at the carbon dust that carbon refractories upper berth one deck 3 ~ 5mm is thick.Temperature in rotary hearth furnace is 1350 ~ 1450 DEG C, and pelletizing residence time in rotary hearth furnace is 10 ~ 20 minutes, is then discharged at discharge port by discharging machine.The product of discharging sends into magnetic separator magnetic separation after cooling, fragmentation, and after choosing, magnetic substance is pearl iron, and non-magnetic substance is molten point slag.Its composition is in table 1,2,3.In acid tolerance response tank, add the hydrochloric acid 400L that concentration is 18%, then add 50kg molten point of slag, be heated to 50 DEG C, react after 1.5 hours and filter, obtain scandium content be 28.4mg/L contain scandium leach liquor 350L, leaching yield is 90.1%.
Table 13 the 5th kind of iron red mud composition
Table 14 pearl ferrous components
The molten point slag ingredient of table 15
Embodiment 6
By Fe
2o
3content is that the additive of iron red mud, weight to be the coal dust of iron red mud weight 20% and weight be iron red mud and the coal dust weight summation 3% of 63.7% mixes to mixer through Belt Conveying, and regulates mixing material moisture to 8%.The mixing material mixed is made carbonaceous pelletizing through Belt Conveying to pair roller ball press, and pressure is 17MPa, and pelletizing is of a size of 40 × 30 × 21mm pillow ellipsoid.Green-ball after drying single berth on the carbon refractories of rotary hearth furnace, in advance at the carbon dust that carbon refractories upper berth one deck 3 ~ 5mm is thick.Temperature in rotary hearth furnace is 1350 ~ 1450 DEG C, and pelletizing residence time in rotary hearth furnace is 10 ~ 20 minutes, is then discharged at discharge port by discharging machine.The product of discharging sends into magnetic separator magnetic separation after cooling, fragmentation, and after choosing, magnetic substance is pearl iron, and non-magnetic substance is molten point slag.Its composition is in table 1,2,3.In acid tolerance response tank, add the hydrochloric acid 400L that concentration is 18%, then add 50kg molten point of slag, be heated to 50 DEG C, react after 1.5 hours and filter, obtain scandium content be 28.4mg/L contain scandium leach liquor 350L, leaching yield is 90.1%.
Table 16 the 6th kind of iron red mud composition
Table 17 pearl ferrous components
The molten point slag ingredient of table 18
Claims (5)
1. use rotary hearth furnace pearl iron process to fully utilize a method for iron red mud, the method mainly comprises:
(1) iron red mud after oven dry, carbonaceous reducing agent, the mixing of additive mixer are obtained compound, wherein the amount of allocating into of carbonaceous reducing agent is 10 ~ 20% of red mud weight ratio, and the amount of allocating into of additive is 1 ~ 3% of compound weight ratio;
(2) add in compound account for compound weight ratio 8 ~ 12% water, through mixer mixing after make pelletizing with pelletizer, dry;
(3) at the carbon dust that bottom refractory upper berth one deck 3 ~ 5mm is thick, by the pelletizing individual layer after drying or double bunk on carbon dust, by rotary hearth furnace reduction, cooling, fragmentation, magnetic separation, pearl iron is obtained and containing scandium molten point of slag;
(4) add in hydrochloric acid containing the molten point slag of scandium, react after 1 ~ 3 hour and filter, must containing the leach liquor of scandium;
The all iron content of described iron red mud is 25 ~ 52%, Sc
2o
3content is 50 ~ 150ppm, Al
2o
3content is 15 ~ 25%, SiO
2content is 5 ~ 10%, TiO
2content is 3% ~ 10%, CaO content is 1 ~ 5%, Na
2o content is 4 ~ 8%.
2. method according to claim 1, is characterized in that, described carbonaceous reducing agent is coal dust or coke powder, and fixed carbon content is greater than 80%, and ash content is no more than 10%, and granularity is less than 80 orders.
3. method according to claim 1, is characterized in that, described additive comprises CaO, CaF
2and Na
2cO
3.
4. method according to claim 1, is characterized in that, in described step (3), reduction temperature is 1350 ~ 1450 DEG C, and the recovery time is 10 ~ 20min.
5. method according to claim 1, is characterized in that, described concentration of hydrochloric acid is 18 ~ 30%, and itself and molten liquid-solid ratio of dividing slag are 8:1, and temperature of reaction is 50 ~ 80 DEG C.
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| KR20150072935A (en) * | 2013-12-20 | 2015-06-30 | 주식회사 포스코 | Method and apparatus for manufacturing molten iron |
| CN104988321B (en) * | 2015-08-04 | 2017-04-05 | 江苏省冶金设计院有限公司 | The method and system of comprehensive utilization red mud |
| CN106148683B (en) * | 2016-08-01 | 2018-07-10 | 江苏省冶金设计院有限公司 | Prepare the method and system of red mud pelletizing |
| CN106222355A (en) * | 2016-09-13 | 2016-12-14 | 江苏省冶金设计院有限公司 | The pyrolysis of a kind of high efficiente callback lateritic nickel ore dry bulb group and reduction reaction system and method |
| CN106222353A (en) * | 2016-09-13 | 2016-12-14 | 江苏省冶金设计院有限公司 | A kind of fume afterheat recycling type lateritic nickel ore direct-reduction produces granulated iron system and method |
| CN106191363A (en) * | 2016-09-13 | 2016-12-07 | 江苏省冶金设计院有限公司 | The processing system of a kind of wet piece of lateritic nickel ore and method |
| CN106191364A (en) * | 2016-09-13 | 2016-12-07 | 江苏省冶金设计院有限公司 | A kind of system and method utilizing wet piece of lateritic nickel ore direct-reduction to produce granulated iron |
| CN106811596A (en) * | 2017-01-17 | 2017-06-09 | 江苏省冶金设计院有限公司 | A kind of method for preparing high-iron bauxite pelletizing |
| CN106916941B (en) * | 2017-03-13 | 2018-06-05 | 北京科技大学 | A kind of method that production rare earth is separated using iron content rare-earth original ore |
| CN109402386B (en) * | 2018-10-31 | 2021-01-26 | 安徽工业大学 | Composite additive for promoting recovery of iron and aluminum in red mud and preparation and use methods thereof |
| CN109439894B (en) * | 2018-10-31 | 2020-09-01 | 安徽工业大学 | Method for recycling iron and aluminum in red mud by utilizing waste resources |
| CN109970368A (en) * | 2019-04-11 | 2019-07-05 | 东北大学 | A kind of method that the melting and reducing dealkalize of iron red mud vortex mentions the direct cement of iron |
| CN110863114A (en) * | 2019-11-22 | 2020-03-06 | 东北大学 | Method for recovering iron by using high-iron red mud and method for extracting aluminum by using high-iron red mud |
| CN111389859A (en) * | 2020-03-20 | 2020-07-10 | 安徽工业大学 | Method for recovering iron powder by direct reduction of red mud |
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| CN102199681A (en) * | 2011-04-28 | 2011-09-28 | 北京科技大学 | Method for separating and enriching iron and rare earth in rare earth crude ore containing iron |
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